CZ189298A3 - Microcell polyurethane elastomer containing urea groups and processes for its production and use - Google Patents

Abstract

The invention relates to a microcellular PU elastomer with improved dynamic-mechanical characteristics, based on an isocyanate component consisting essentially of 4,4'-MDI and other standard components. The elastomer in question has a physical-chemical structure characterised by a one- or two-peak signal next to the low-molecular main signal for an (apparent) molar mass of greater than 250,000 g/mol as measured by gel-permeation chromatography from a solution of the microcellular PU elastomer produced at 90 DEG C in N,N-dimethylformamide with 1 % di-n-butylamine, against polymethylmethacrylate (PMMA) as the standard, the signal being reduced or eliminated following addition of lithium chloride to this solution. The elastomer has a urea content of 14-18 wt %. Also disclosed are a process for producing such a microcellular PU elastomer with improved dynamic-mechanical characteristics and the use of said elastomer to produce damping elements.

Description

The invention further relates to a method of producing such a microcellular polyurethane elastomer and also to its use.

So far defective.........status........technique

The production of cellular polyurethane elastomers, their use, as well as their mechanical and chemical parameters, are sufficiently described in the Kunststoffhandbuch.

After 1yurethany. 1968, 1983 and 1993 by R. Vieweg and A and possibly G. Oertel, Carl Hanser Verlag, Munich.

Polyurethane elastomers are fundamentally characterized by better damping properties in compression compared to analogously used types, which makes them ideal for use in rubber components, especially in the automotive industry, with their distinctly different volume systems that ^absorb vibrations and shocks. A typical example of a microcellular polyurethane elastomer for the above-mentioned application is the reaction product of 1,5-naphthyl isocyanate and ^{polyethylenglycoal} adipate with an average molecular weight of 2000 g/mol, which is reacted as an NCO prepolymer with a 50 percent aqueous solution of fatty acid sulfonate.

- ?

• · • · ·· • · fl • · 4 ·· · ·· ·· » · · fl » · · · • · · · fl • · fl ·· ·· containing an activator. Since the performance level of this basic recipe is insufficient in terms of its damping characteristics and also the usual static and dynamic performance parameters, some other efforts are still known from the literature, which replace the mentioned 1, 5-naphthyl diisocyanate with the more cost-effective and clearly easier to handle 4,4'-diphenylmethane diisocyanate for the excellent properties of the elastomer, while they are calculated

Characteristic differences between elastomers based on and in micromolecular formulations in the Journal of Elastomers and Plastics in the article by E. C. Prongheuer, J. J. L, i ndsay ye and essential disadvantages of microcellular polyurethane elastomers based on 4,4'-MDI are stated a considerably high degree of attenuation and a considerably settling behavior under dynamic loading, which clearly decreases the properties, compact polyurethane 4,4'-MDI in general and especially listed from 21, April 1980 H. Kleimann. As

NDI and

are Vo 1 .

from above does not ultimately lead in comparison

NDI for faster material abrasion.

It is stated that, despite these generally known disadvantages, there are, as already known from the literature, attempts to use 4,4'-MDI as a substitute isocyanate component for NDI in microcellular polyurethanes. However, these attempts are limited only to the use of new material components, in particular high-molecular-weight polyhydroxy compounds, with the help of which the resulting microcellular polyurethane elastomers are to achieve certain advantageous properties.

Thus EP-A-0496204 describes a method for producing cellular polyurethane elastomers using polyethercarbonatediol, which contains polyoxytetramethylene glycol residues with an average molecular weight of Mn 150, as an oligomeric compound, which improves mechanical properties, especially ductility, static residual up to 500 g/mol, and compressive deformation, even at low temperatures. ⁰ C, is not a correlating component (see.

• ·· · · · · · · · · · · · · « · · · · • ·· · ··· ·

Kunststoffhandubuch, volume VII, a 1993) only an average deformation is obtained.

Polyurethans, 1966, 1983 static residual pressure

EP-A-0243832, which also claims the use of 4,4'-MDI in conjunction with water as a blowing agent for the production of microcellular polyurethanes, has as its essential inventive use of polycondensates containing polyoxytetramethylene glycol with short hydroxyl chains and as oligomer idea groups of a 1 i f a t i c f t e dicarboxylic acid of a polyhydroxy compound with the aim of obtaining a polyol containing ester groups, easily doseable by means of a pump, for cellular or compact polyurethane elastomers with improved mechanical and hydrolytic properties. However, data on the residual degree of deformation under static or dynamic loading, which is usually characteristic of vibration-resistant materials, are missing. The connection between the content of the invention and the permanent deformation relevant for shock-absorbing materials is therefore not apparent under static and dynamic loading.

DE-A-3613961, on the other hand, describes a microcellular polyurethane elastomer based on 4,4'-MDI which, due to a defined composition of an oligomeric polyhydroxy compound consisting of copolymers of polytetrahydrofuran and 6-caprolactan, has mechanical properties which represent a favorable compromise between static strength and dynamic load capacity. Despite the use of expensive polyol base materials, the performance gain achieved in terms of stability, de Mattia bending strength and residual deformation at 50% compression is only small. For example, the specific values for residual deformation, which are directly related to the size of the bones, show only a practical and relevant dynamic reduction, using the findings of the invention for practical purposes.

Also, the insufficient improvement of the stability and bending strength criteria according to de Mattia does not seem to be sufficiently suitable for evaluating dynamic properties close to practice, since with partial improvements in characteristics it allows to display only insufficiently differentiated objectively existing performance differences between polyurethane elastomers formed from MDI and NDI.

In addition to the improvement of the static and dynamic characteristics and dynamic stability by the appropriate choice of oligomeric polyhydroxy compounds, described in the above-mentioned DE-A-38 1 396 1 , the isocyanate component also has a decisive influence, as is well known for example from the already discussed NDI, leading to polyurethane products with excellent static and dynamic elastomer properties. Thus, the use of the isocyanate 3, 3'-dimethyl-4,4'-biphenyl diisocyanate (TODI) and paraphenylene diisocyanate (PPDI) also leads to microcellular and compact polyurethane elastomers with excellent static and long-term elastic properties. The reason for this is said to be the excellent crystal 1 and start ·. The ability of hard segments formed from urea or urethane groups, which further leads to their good separation from soft segments formed from oligomeric polyhydroxy compounds. The poorer crystallinity of urea or urethane groups on 4,4'-MDI due to their strongly different spatial structure is, on the contrary, considered to be the decisive reason for the clearly deteriorated static and long-term elastic properties.

In DE-A-195 09 8 1 9, an OH prepolymer is also used in addition to NCO. According to our findings, this variant allows good relaxation, i.e. no damage to the part at the end of the deformation, and good technological • 0 • · 0 0 0 0 • · · 0 0 0 · 0 · 0 • 000 0 0 ··· · *00 • · · · 0 · · · ·00 0 · • 0 0 · · · · 0 0 0 • •• 00 00 00 0· ·· manufacturability, but the residual compressive deformation and the resistance to further tearing are completely inadequate.

P.o,.ds.t..a.t and........v.other . t e z u

The present invention is based on the task of developing a microcellular polyurethane elastomer based on 4,4'-MDI, which is more cost-effective and much easier to handle than NDI, TODI and also PPDI, as the main isocyanate component, which has, independently of the type of oligomeric polyhydroxy compound used, significantly improved static mechanical characteristics, in particular residual pressure deformation and dynamic shrinkage, and is therefore particularly suitable for shock absorption systems in the construction of motor vehicles.

This object is achieved according to the invention by producing a microcellular, urea-containing polyurethane elastomer, hereinafter referred to as a microcellular PU elastomer, with a urea content of 14 to 16% by weight, based on 4,4'-MDI as the main isocyanate component. and a structure which is characterized in addition to the low molecular weight main signal for the molecular chain of the elastomer by a signal which consists of one or more zones with an apparent molecular weight of more than 250,000 g/mol, measured by gel permeation chromatography (GPC) from a solution of microcellular PU-elastomer, formed in N, N-dimethylformamide with 1 percent di-n-butylamine at 90 °C with respect to polymethylmethacrylate (PMMA) as standard, and which is reduced or lost by the addition of lithium chloride to this solution, the structure being formed by the addition of Brönstedt or Lewis acid reagents in an amount of 0.01 to 5 wt. %, based on the weight of components a), b), e) and optionally

c) .

• · • · ·· • · 1 • · 4 · · 9 9

999 9 9 4 • · 4 » · · • · » · 9 » · 4

99 9 9 9

4

The subject of the invention is therefore a microcellular PU-elastomer based on

a) isocyanate components consisting essentially of

4,4'~di f eny1me t hand i isocyanate s

b) at least one oligomeric polyhydroxy compound with an average molecular weight of 1000 to 5000 g/mol and a functionality of 1.7 to 3, preferably 2,

c) optionally a low molecular weight chain extender and/or crosslinking agent and

d) the means of propulsion and also

(e) catalysts and, where applicable,

f) auxiliaries and/or additives.

which has a content as an amount arising from urea of 14 to 18 wt. % urea with a total diphenylmethane diisocyanate, which is defined by the formula Ci 4 Hi 2 OM2 , percentage, based on the total amount of elastomers after urea formation and a physicochemical structure which is characterized in addition to the low molecular weight 111 from one or more signal zones by a signal occurring with an apparent molecular weight of more than 250,000 g/mol, measured by gel permeation chromatography (GPC) from a solution of microcellular PU-elastomer, formed in N, N-dimethylformamide with 1 percent di-n-butylamine at 9 0 °C with respect to fc polymethylmethacrylate (PMMA) as standard, and after the addition of lithium chloride to this solution decreases or • · • · ♦ · · ·

I · · ft · · ·

I · · 4 » · · 4 • · · · • · · · > · · 4

I · · · • · · · 4 • · 4 • · · · lose.

formed by the addition of Brónstedts.

acidic reagents in an amount of 0.01 to the weight of components a), b), e) and optionally Lewis % by weight... based on

The invention also provides a method for producing such a microcellular PU elastomer with improved dynamic-mechanical properties, which is characterized by adding Brönstedt or Lewis acid reagents in an amount of 0.01 to 5 wt. % based on the weight of components a), b), e) and optionally c) and performing a tempering of the microcellular polyurethane elastomer at 100 to 120 °C for up to 24 hours, as well as the use of microcellular

PU-elastomers for the production of damping elements.

exploration of multiple variants of the physical structure of 4,4'-MDI, it was found that

Surprisingly, due to their different chemical and structural properties, microcellular PU-elastomers characterized by the described SPC zones achieve minimal residual compression set compared to microcellular PU-elastomers at 80 °C. This residual compression set, measured at 60% compression after 22 hours at 10 °C, correlates with the shrinkage after dynamic long-term loading, which is important for practical requirements, so that a small residual compression set also corresponds to the desired low shrinkage. The production of various chemical structures of the elastomer based on 4,4'-MDI can be carried out in a known manner, in particular by using various measures which, for example, slow down the addition reaction of isocyanate, by using various basic components, such as polyester groups, and/or polyethylene groups, by changing the physical action of the various such groups, for example by suitable means, such as suitable conduction.

99 > 9 9 4 » · · · • · · · 4 • · 4

9 9 9 by appropriate additional heat treatment or by using substances which the formation of this structure requires and which act as nucleating agents for the structures according to the invention. These measures for the formation of the structure according to the invention can also be used in combination to enhance the effect.

P U-e1 a s t o m e r in di-n-butylamine at

The GPC solutions required to characterize the structures of the invention are prepared by dissolving the microcellular sample in 1% N,N-dimethylformamide (DMF) at 90° C. The GPC itself is carried out in a known manner with this solution using a column set with a suitable pore size of trastyrage and is calibrated with a PMMA standard of defined molecular weight.

molecular weight in the description of the zone according to the invention means that these g/mo.1

The characteristic structures of typical high-molecular structures of more than 250,000 are not entirely or partly caused by chemical, but primarily by physical bonds, since they are eliminated or reduced by the presence of 0.1 mol of LiCl per liter of solution (i.e. a solution of 0.1 mol of LiCl in the DMF/amine mixture is available). The GPC itself is carried out in the DMF/amine solution on the described column set with or without LiCl - Detection can also occur by measuring the refractive index as well as by UV absorption. If an unexpectedly small residue of cellular PU elastomer remains undissolved, it is also possible to demonstrate the structure according to the invention in the chromatogram of the dissolved fractions without any problems.

In addition to the characterization by GPC, the structures according to the invention can preferably also be described additionally by means of the melting range, determined by differential decomposition calorimetry (DSC) when heating at 20 °C/min., 130 °C. as the minimum lower limit, up to 230 °C, as the minimum upper limit, after tempering the microcellular PU elastomer before measurement at 100 to 120 °C after • · » · ·

I · · ·· » · « « » · · « ·· ·· • · · · · ♦ 4 • « ·« ··· · 4 • · 4 ·· ·· for a period of 8 to 24 hours.

It is generally known that it is possible to characterize structures using DSC and GPC, that it is generally possible to produce different structures from polymers of the same chemical composition, which are essential in terms of properties and not only the chemical composition itself affects the properties. A new such structure is viewed as a new modification of the substance, as follows from well-known textbooks on the description and characterization of polymers, for example from the book Polymers on 1ytik by Martin Hoffman, Herbert Krohmer and Rainer Kuhn, published by Georg Thieme Verlag.

p o o i s o v a x a It is also known.

When the modification of substances in microcellular PU elastomers is produced according to the invention, which can be characterized under specified conditions by GPC and optionally also DSC, these elastomers have a compression set at 80 ^° C. shrinkage.

unexpectedly low residual and low dynamic range values

It is known that there are also quite general connections between such structures and properties of polyurethane elastomers and DSC, for example, describes the molecular degree of order as a structural quantity. Such connections are for example in the journal Kautschuk und Gummi, issue 7/8 2, in the article by Th. Timm. From

PU-elastomers described

Kunststoffe, 35th edition of generally known knowledge about properties is in no way derived.

The connection between the invention of the claimed structures results in the required good properties

It can be shown experimentally that cellular PU elastomers with the same chemical composition but not with the structures according to the invention only provide undesirably high residual compression set and dynamic shrinkage. However, the chemical composition cannot be chosen completely freely, but the optimum urea content in the microcellular PU elastomer must be maintained in the range of urea concentration up to 18% by weight. Within this range, the residual compression set and dynamic shrinkage are reduced only when the structures according to the invention have been created. The basis for elastomers from

NCO-

and OH-prepolymers, e.g. k1 ad according to DE-A-195 09 8 19, cannot create structures according to the law1 I'm climbing. In continuity and on that's it receives only insufficiently high residual deformation in pressure and small

resistance to further tearing.

The production of cellular PU elastomers based on 4,4'-MDI with such a structure that is favorable for properties is not yet known. The structures according to the invention characterized by 6PC have not yet been described for microcellular PU elastomers.

Polyurethane coats

In the Kunststoffhandbuch, Volume VII, 1993, only the creation of additional chemical crosslinking sites is described as an important means of improving the residual compression set in soft foam systems and compact polyurethane elastomers, for example by means of a limited increase in the functionality of the raw materials forming the polyurethane, or by means of sulfur, peroxide and even cyanate vulcanization.

However, for microcellular PU elastomers, this measure means an increase in the residual deformation under compression and shrinkage.

worsen, it and dynamic

The usual greater chemical crosslinking loses its significance for improving the residual compression set in the case according to the invention and it is completely unexpected that the structures according to the chemical crosslinking and dynamic shrinkage of the invention without greater compression set reduce the residual compression set.

As a result, it was found that with reaction-retarding substances, which are introduced into the reaction in limited quantities • ·· ·Φ φφ φφ φφ ·· · φφφ φ φ « • ΦΦΦ · φφφφ φ φφφ • · φ φ Φ · · ·· · · <

• Φ Φ Φ <

ΦΦΦ ΦΦ ΦΦ ΦΦ Φ· ·Φ mixtures, the structures desired according to the invention can be formed.

The addition of these reaction-retarding substances to the reaction mixture can occur at the beginning or during the production of the prepolymer and/or at the beginning of the foaming.

Substances that have this effect in polyurethane chemistry are Lewis acidic reagents, which are used primarily to adjust the reaction times required by the production process.

possibly

to achieve s t a b i I am a law student after 1yurethans contain and also zocyanatan. Between they count for example be nz o y 1 c h 1 o r i d , d i ethyl eng 1 y.k o 1 ~b i s --c h 1 or o rnr avenčan. Feature1 i n a p -1 o 1 u o 1 su1f o nova, acid 1 i nan-a1ky1benzensui f ono vá a their salts with ethanol, ace t y laceton, et h y1s s s t e r sour and now acetic acid

and mineral acids, such as phosphoric acid and hydrochloric acid.

The type and amount used depends on the use case.

The production of structures according to the invention, which are characterized in the above-mentioned manner by means of 6PC and optionally also DSC, is the main criterion.

Surprisingly, it turns out that these structures can be produced particularly easily using a so-called latently, not time-dependent, catalytically active catalyst system. These catalysts are only active after a certain time, after the addition of reaction retarders and reaction accelerators or substances which carry chemical groups from reaction accelerators or reaction retarders to the molecule. A suitable material for this is the monoethanolamine salt of the components, since polyurethane and urea, can be, for example, mixtures • ·· 44 ·· • 4 · 4 4 4 4 • 444 · · ··· • » · · · 4 4 · · · · · • 4 · · · · · • 44 ·· 44 44 ·· • · · · 4 • 4 44

4 4 4 4

4 4

44 n-alkylbenzenesulfonic acids with C0 to C18.

These substances are used in amounts of 0.01 to 5 wt. %, based on the weight of component c).

slowing down the reaction with preferably 0.05 to 2 a) , b) , e) and optionally

By simply mixing the reaction components in a closed mold, carried out by simple foaming in hand-held kits or preferably in low-pressure foaming machines, the described structures can be created in microcellular PU-e 1 and s to m e r .

The production of structures according to the invention is greatly facilitated if the tempering of the microcellular PU elastomers begins immediately or at the latest within 2 hours after removal. Characterization of the structures according to the invention allows their relative quantification. When combining the measures of using reaction retarders or molecular groups with an immediately subsequent thermal treatment immediately after removal, for example, the ratio of the zone above 250,000 g/mol in GPC to the main zone of the PU elastomers in the region below 250,000 g/mol increases. This higher ratio indicates a higher content of oodle structures in the resin, which is not used or only insufficiently if tempering is started only after 2 hours after removal. Due to the higher amount of structures according to the invention in the microcellular PU elastomers, the residual compression deformation and dynamic shrinkage are reduced.

The advantage of non-deformable removal is that these measures do not disadvantageously remove the mold during the production cycle.

Surprisingly, in components a), reaction product 4.4, it turns out that the content of urea dispersed

d) and possibly e) and f), for example as

-MDI with water, helps to create structures according to ·· · ·· • · » · · ft · · · · » · · « k · · I ·· ·· ·· k · · « k · · · • · · · <

• · « • · · · of the invention. The urea content must be between 0.05 and 5% by weight, preferably 0.1 to 1% by weight, based on the total elastomer. The production of this dispersed urea is carried out by adding a suitable amount of isocyanate to the aqueous crosslinking components.

The percentage of urea is defined as the amount of urea formed from MDI with the general formula Ci 4 Hi 2 ON2 , based on the total amount after urea formation. The escaping stoichiometric amount of CO2 isocyanate does not then result in the formation of the total amount of urea from water and is also explained in more detail in the calculation formula for the total amount of urea in microbubble PU elastomer in example 1.

The urea required to form the structures of the invention can also be produced by other means, for example from MDI and an amine, for example 4,4'-diphenyl methanamine.

In addition to the characteristic of the residual deformation in compression as a statistical data for the resetting of the elastomer and better characterizing the test values of the reduction as a correlation quantity for the practical requirements of the impact absorption system under dynamic conditions., such as the resistance of the strength assessment in the automotive industry, the characteristics determined serve to characterize the elastomer characteristics of tensile strength. relative elongation at break and against further tearing. Especially for the demolding and mechanical stability under dynamic loading, knowledge of these characteristics determined under static conditions is important, with a significant role being attributed to the level of resistance against further tearing.

tearing

It is known to determine the value of resistance to further compact polyurethane in the first line by the amount of urea, determined by the recipe, that is, to fix it only ·· » · · 4 » · ·· ·· · 4 • · 4 ·· ·· • ·· • · · · · · • · 4 • · 4 ·· ·

which essentially creates a hard segment through the main reactions, which is clearly needed for the driving process

Microcellular PU polymers, in the polymer structure and the formation of cells between isocyanate and water, contain new structures based on urea. Increasing the content of the hard segment from urea, which can be realized by increasing the isocyanate content, or by increasing the molecular weight of the 1-mer polyhydroxy compound while the isocyanate content remains unchanged, leads, in analogy to compact elastomers, to improved resistance to further tearing and tensile modulus values. However, this option is only of limited use, because firstly, the material-specific hardness during compaction increases unexpectedly at a given density, the development of carbon dioxide and the accompanying formation of urea increase, so that even with an acceptable hardness during compaction, an expansion effect occurs in the removed shaped bodies with mechanical damage due to the formation of cracks.

dynamic forming, mass Good

Surprisingly, it has been found that the structures according to the invention are particularly effective for reducing residual tensile deformation and shrinkage, associated with good demoulding conditions only in conjunction with a urea content of 14 to 18%, so that mechanical damage to the molded parts made of microcellular PU elastomer does not occur, especially when demoulding complicatedly designed parts.

The urea content between 14 and 18% by weight can be adjusted using water from the recipe according to the formula given in Example 1. The amount of urea that is optionally added or produced for • ·· ·· ·· ··

9 9 9 9 9 9 9 9

999 9 · 999 9 9 99

9 999 99 99 999 9 9

999 9999 999

999 99 99 99 99 99

-15ροneeds to create structures are included in the total quantity with respect to the 1st 1st 2nd 3rd 4th 5th 6th 7th 8th 9th 10th 11th 12th 13th 14th 15th 16th 17th 18th 19th 20th 21st 22nd 23rd 24th 25th 26th 27th 28th 29th 30th 31st 32nd 33rd 34th 35th 48th 59th 61st 35th 58th 62nd 63rd 64th 65th 66th 67th 68th 69th 79th 71st 72nd 73rd 74th 75th 76th 77th 78th 79th 88th 89th

The urea content is usually negligible, however, even before foaming.

In the urea concentration range below 14 wt. %, the structures according to the invention cannot be produced safely by the measures described so far and/or their effect on reducing the residual compression set and dynamic shrinkage is limited. In the concentration range above 18 wt. %, the formation of this structure is also not safely possible. In addition, the reaction between water and isocyanate to form the expansion effect of the carbon dioxide formed at the same time is so great that unwanted cracks can form in the shaped bodies after demolding.

For the production of microcellular PU elastomers according to the invention, in addition to the substances already mentioned, known starting components are used, which are listed individually below:

a) The isocyanate components a) according to the invention consist essentially of 4,4' MDI.

In addition to TSF.O, they may contain other organic and/or modified organic polyisocyanates. In addition to 4,4'-MDI, 2,4'- and/or 2,2'-MDI are preferably used, as well as mixtures of MDI isomers with polyphenylmethylene polyisocyanate (PHO-MDI) and mixtures of PHO-MDI and polyphenylmethylene polyisocyanate.

Diphenylmethane and chemical reactions can also be used as isocyanates,

MDI. For example, polyisocyanates based on diphenylmethane containing ester, urea, biuret, called modified, that is, products are di- and/or structures, allophane and preferably carbodiimide, isocyanuric and/or urethane • · • 9 • · » · • 9 · • 9 9 · · · 9 9 9 4 • 9 9 9 9 9 9··· 9 999 ·· · · 9 99 ·· 9 · 9 9 9 4 • '99 9 9 9 9 9 994 ····· 99 ·· 99 9· s k u ρ ί n y .

Based on the dipheny í-methane. considerations of the urethane group ρ o 1 yizocyanatanys «5 r ^γ Ι RU Γ In the content ;j í c í up to 33 . δ comes to the aromatic % henotn. .

with an N C O content of preferably 4 to 8% by weight, for example with low molecular weight diols, triols, oxyalkylene glycols, dioxyalkylene glycols or polyoxyalkylene glycols with a molecular weight of up to 800 modified 4,4' MDI, wherein di- or polyoxyalkylene glycols, which can be used individually or as mixtures, are diethylene, dipropylene, polyethylene, polyoxypropylenepolyoxyethylene glycols. Suitable are those containing N C O groups with an N C O content of preferably 4 to 8% by weight with polyesters based on dicarboxylic acids with 2 to 12 carbon atoms and dihydric alcohols. Polyhydroxy compounds can be used as polyesters.

and polyoxypropylene also for polymers % wt., for example on

Analogous to modified polyethers, polyesters can also be used with esters or ethers modified with

Also, isocyanates containing WCO in a content of 3 to 33.6% by weight have proven to be effective.

with mixtures of liquid carboxyls of the 1-diimide group of the isocyanurate ring, for example based on 4,4'-,

2,4'- and/or 2,2'- MDI and also the corresponding isomeric mixtures, for example of 4,4'- and 2,4'-, Roh-MDI and 1,2-diisocyanates and Roh-MDI.

The use of polymers of polyisocyanates and representatives of components <b) and optionally (c) with an isocyanate end group instead of isocyanates or together with them in a mixture is also possible.

• ·· • · · 4 4 4 4 4 4 4 • 444 · 4 4 4 4 · · 4· • · 4 4 4 44 4444 4 • 44 4444 444

44444 44 44 44 44

In the know d i i I am a child. with to 15 moles you s o c s f u n k č η í ho d i i z c akyanatan) - Quantity in •high however must be about me woman like that, that it is cy . ^T í .. -n-butyl amine contained yet

They can also use polyisocyanates together, based on the functional polyisocyanate in N,N-dimethylformamide with at least partially dissolved product. Larger amounts must generally be balanced by the high functional isocyanate with compounds and/or isocyanates that are on average less difunctional than the isocyanate, so that further chemical crosslinking of the product is avoided.

As oligomeric polyhydroxy compounds b) there are also essentially linear compounds with a molecular chain, polyoxytetramethylene glycols, in particular glycols, essentially polyoxytetramethylene glycols modified with carboxyl and ester groups, essentially polyoxytetramethylene glycols modified with carboxyl and ester groups, and polyoxytetramethylene glycols with an average molecular weight of 1000 to 5000 g/mol.

Also polyoxytetramethyl glycols as well as derivatives of polyoxytetramethyl glycols, carboxy groups and ester groups, can be used as components or in the form of mixtures of polyester polyols individually or in combination. They are also mixtures.

Suitable, essentially linear polyester polyols can be prepared, for example, from dicarboxylic acids with 2 to 12 carbon atoms and dihydric alcohols. Dicarboxylic acids include, for example, succinic acid, glutaric acid, adipinic acid, and phthalic acid.

acid and on cork, acid azelaová,· a r o rna t i c ké dicarboxylic a s s e 1 i n y, like acid also on i z o f t a 1 o v a and acid and na

• · • · ·· ·· • ·

- 18 terephthalic. Dicarboxylic acids singly or as mixtures. It may be advantageous to use corresponding carboxylic acid derivatives in the production of polyesterpolyols, such as carboxylic acid esters, carboxylic acid anhydrides or carboxylic acid chlorides. Examples of dihydric alcohols are those with 2 to 16 carbon atoms, preferably 2 to 6 atoms, such as ethylene glycol, diethylene glycol, pentanediol, 1-1.5-hexanediol,

2,2-di methylpropanediol 1-1,3, propandiol 1 -·-1 , 3 and Depending on the desired properties, alcohols can be used alone or optionally with each other, glycine, fu tandiol 1 -1 , 4, decandiol 1 ·-1 , 10, dipropylene glycol 1 -1 , 3 and a two-component mixture.

Also suitable are polyesters containing hydroxyl groups, carbonic acids with the above-mentioned glycols, especially with 4 to 5 carbon atoms, such as butanediones of 1-1.4 and/or hexanediones of 1-1.6, condensation products of hydroxycarboxylic acids, for example ω-hydroxypronic acid and preferably polymerization products of lactones, for example optionally substituted ε-caprolactones.

As polyester polyols, 1,4-butane-1-polyethylene glycol and 1,4-butane-1-polyethylene glycol are preferably used.

©thanoldiol-polyadipates, 1,6-hexanediol-neopentylglyco i polyadipates, 1,6-hexanedio1-1,4-butanedio 1-po 1adipates and po 1y capro o!act a n y.

Suitable polyoxyalkylene glycols containing ester groups are polycondensates of organic, preferably aliphatic dicarboxylic acids, in particular adipic acid with polyoxymethylene glycols with an average molecular weight of 162 to 600 and optionally aliphatic diols, in particular butanediol-1,4. Also suitable polyoxytetramethylene glycols ·· ·· · 0 • 0 0 0 0 • 0 0 0 · · • 0

- 19 • 000 • · • · ·· · ··

0 0 0

0 «

0 0

0 0 I

0 · • 0 00 containing ester groups are polycondensates formed by polycondensation with g-caprolactone.

Suitable polyoxyalkylene glycols containing carboxyl groups, essentially polyoxytetramethylene glycols, are polycondensates with alkylene, optionally aryl carbonates or biphosgene.

In the production of microcellular PU elastomers, low molecular weight chain extenders and/or crosslinking agents c) can be used.

Suitable chain extenders and/or crosslinkers have a molecular weight of less than 500, preferably 60 to 400. For example, alkanediols with 2 to 12 carbon atoms, preferably 2, 4 or 6 carbon atoms, such as ethane-, 1,3-propane-,

1,5-pentane-, 1,6-hexane-, 1,7-heptane-, 1,8-octane,

1,9-nonane-, 1,10-decanediol and preferably 1,4-butanediol, di- and 1-alkylene glycols with 4 to 8 carbon atoms, such as diethylene glycol and dipropylene glycol, and di- to tetrafunctional polyoxyalkylene polyols with a molecular weight of up to 500. However, branched-chain alkanediols and/or unsaturated alkanediols with usually not more than 12 carbon atoms, such as 1,2-propanediol, 1,2-methyl-,

2,2-dimethylpropanediol-1,3, 2-butyl-2-ethylpropanediol-1,3, butene-2-diol-1,4 and buty n-2-diol-V,4, terephthalic acid diester with glycols with 2 to 4 carbon atoms, such as bis-ethylene glycol or butanediol-1,4 terephthalic acid, hydroxyalkylene ether of hydroquinone or, for example, 1,4-di (β-hydroxyethyl) resorcinol, 2 to 12 carbon atoms, such as

2-a m i no pr o pa no 1 and 3-a m i no-2., 2-di methyl resorcinol, as a l k a η o 1 a rn i n y s e ethanolamine.

propanol, N-alkyldi- and 1-kanolamines, such as N-methyl • <

• · • · • · • · · · « m · · ···· • ··· · 9,999 9,999

999 99 99 9999 9

9 9 9 9 9 9 9 9 9

99999 99 9 9 99 99

- 20 N-ethyl-diethanolamine.

High-functional crosslinking agents are, for example, high-functional alcohols, such as glycerin, trimethylolpropane, pentaerythritol and trihydroxycyclohexane, as well as trialkoolamines, such as triethanolamine.

Alkyl-substituted aromatic polyamines with a molecular weight of 122 have proven to be preferred as chain extenders and are therefore preferred.

<3 Z 400, especially primary aromatic diamines, which content of it In o r t ho polo that at least one of the amine groups and 1 k y 1 subst i t u e n t which prevents by steric b a n d i n g r e amino activity groups that are at ambient temperature i c u t e and are and 1e and after partially, preferably completely behind condition

processing miscible with high molecular weight, at least difunctional compounds (b) and N-perethoxylated polyoxyalkylene polyamines (c).

For the production of microcellular PU elastomers, the technically readily available 1,3,5-triethyl-2,4-phenylenediamine, 1-methyl-3,5-diethyl-2,4-phenylenediamine, mixtures of 1-methyl-3,5-diethyl-2,4- and --2,6-phenylenediamines, so-called DETDA, isomeric mixtures of 3,3'-di- or

3,3',5,5'-tetraalkyl substituted 4,4'~diaminodiphenylmethanes with 1 to 4 carbon atoms in the alkyl radical, especially

3,3',5,5' tetraalkyl-substituted 4,4'-diamino-diphenylmethanes containing bound methyl, ethyl and isopropyl residues as well as mixtures of the above tetraalkyl-substituted 4,4'-diamino-diphenylmethanes and DETDA.

To achieve special mechanical properties, it may also be useful to use alkyl-substituted aromatic polyamines in a mixture with the above-mentioned compounds. molecular weight φ φ φ • φφφ • φ «

Φ 4

ΦΦΦ Φ φ • Φ · · · · Φ Φ » φ · · · φ <

Β · ΦΦΦ Φ ♦ ··

Β ΦΦ ΦΦ ΦΦΦ» 4 Β Φ Φ Φ Φ Φ 4 •Φ ΦΦ ΦΦ ΦΦ in ί ο θ mo c η ym i a l k o ho 1 y, front o t n 1 koholy ne b o d i a 1ky1βn g1y ko i y.

two and/or three powers

Low molecular weight chain extenders and/or crosslinkers consisting of low molecular weight di- and/or trifunctional alcohols, di- to trifunctional polyoxyalkylene polyols with a molecular weight of up to 500 and alkyl-substituted aromatic diamines or mixtures of at least ^{two of} the above chain extenders and/or crosslinkers.

d) As a propellant, mainly water, which reacts to form carbon dioxide.

d) is used according to the invention with the addition of Rva and new groups,

The amount of water which may be used is preferably 0.01 to 5% by weight, preferably 0.3 to 3.0% by weight, based on the weight of components (b) to (c).

which are liquids, organic polyisocyanates and ⁰ C. Examples of such are hydrocarbons containing

In addition, other blowing agents customary in polyurethane production can also be used. For example, liquids boiling at low temperatures are suitable, the exothermic polyaddition reaction evaporates. Suitable for this are inert liquids with a boiling point below 100 °C, preferably halogen, preferably fluorine. such as methylene chloride and dichloromonofluoromethane, per- or partially fluorinated hydrocarbons, such as trifluoromethane, difluoromethane, difluoroethane, tetrafluoroethane and heptafluoropropane, hydrocarbons, such as n- and iso-butane, n- and iso-pentane and mixtures of these hydrocarbons, propane, propylene, also technical hexane, heptane.

cyclobutane, dialkyl ethers such as cyclopentane and cyclohexane, methyl and ethyl formate, • · ··· ·· ·· » · 9 » · · · ·

ketones, i and to e.g. k1 and d acetate. perfumed, tertiary a .i k y i a m i p e r f 1 u o r - d i me t hy1 ~ from 1 species amen. Also t h e t h o w n low ý o h heat that's hot

substituted with or without other hydrogens.

fluorinated and/or as an example, mixtures of mutually substituted liquids can be used

The preferred amount of low-boiling liquid for producing these cellular elastic shaped bodies from bonded elastomers depends on the density to be achieved and also on the amount of water used. In general, satisfactory results are obtained with an amount of 1 to 15% by weight, preferably 2 to 11% by weight, based on the weight of components (b) to (c).

e) To accelerate the reaction, catalysts e) are added individually or also to the reaction batch in a mixture with each other.

Preferably, these are organic metal compounds, such as tin salts of organic carboxylic acids, such as dioctoantinate, dilaurantinate, dibutyltindiacetate and dibutyltindi1uranate, and tertiary amines, such as tert-amethylenediamine, N-methylmorpholine, diethylbenzylamine, triethylamine. dimethylcyclohexylamine, diazabicyclooctane, N,N'-dimethylpiperazine. N-methylpiperazine, N,N,N',N'',N''-pentamethyldiethylenediamine or the like.

Further suitable catalysts are amides, such as 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine, tris(dicyclopentadienyl)-s-hexahydrotriazines, especially tris-(N-dimethylaminopropyl)-s-hexahydrotriazines, tetraalkylammonium hydroxides, such as tetramethylammonium hydroxide, hydroxides, such as sodium hydroxide, and alcoholates, such as sodium methylate, alkali salts of fatty acids, and potassium isopropylate, with a long chain of 10 to 15 carbon atoms, and optionally OH activators.

9 9

9 9 9 '7 'Ά

Depending on the reactivity set, the amount is 0.001 to 0.5% by weight, based on the polymer in.

f) In the production of the microcellular PO-elastomers according to the invention, in addition to the other reaction-retarding substances mentioned above, other auxiliaries and additives can be used.

These substances include, for example, surfactants, hydrolysis inhibitors, antioxidants, cell regulators, fire retardants and dyes.

As surface-active substances, compounds are considered which serve to promote the homogenization of the starting materials and are also suitable for regulating the cell structure. One example is emulsifying agents, such as sodium salts of ricinoleic acids or fatty acids and also salts of fatty acids with an amine, for example diethylamine of oleic acid, diethanolamine of stearic acid, diethanolamine of ricinoleic acid, salts of ricinoleic acids, for example alkali or ammonium salts of dodecylbenzene or naphthylmethane sulphonic acid.

voltage í s t a b i 1 i z a t o r y, j a k o s i 1 o xa n -o xa 1 k y 1 e n o vé mixed poly 1yme ry and i n e o· r g a n i c k e poles and also 1 o xa n y, and 1 k y 1 f e η o 1 y, oily a 1 k o h o 1 s, couple and new oils. castor esters o i e i e , if applicable r i c i n o a i. a i o v & & v a β í i n v o 1 e i e n a t u r e c u c u c e r v e n a peanuts it about 1 hour they are regulators cells, like paraffins. oily alcohols and d i rne t h y i ρ o 1 y s i 1 o xa n y Surfactant sub station he got used to it 0 p 0 u ž í v a .j í v quantity 0 .01 to 5 by weight d i 1 s, related to on 100 massive parts 1 s components (b) to (d)

Fillers are known conventional organic and inorganic fillers. These include, for example, inorganic fillers such as • · • ··· • · 4 « · 4 • · · · · · · · · · • ·

I · ··· > tt « » t t 4 ·· tt ·· ··

I · 9 i » 9 · · • · · · 4

9 4 ·· «· siliceous minerals, for example layered silicates such as

anti-gorian, serpentine. and rnf and they were sore, ointment kaz ® o ! i t h .. oxide y metals, such _as n a p r i c i a d to and about 1 i n. oxides. h i i η í k u , o x i d y t i t. a n u , iron oxides a s o i ů i metals. like a horse k 1 a d k ř í d a , Parvt a a n o r g a n i c k e pigments like I'm sorry. r n i k k a d rn i a, s i r η í k i n e c h n a t y. Advantage n e with uses ka o t i n (China C a y) , k r n i c i t a n h 1 i n i t y and c o p r e c i p i t y of e s i r η í k u barnate and silica h 1 i n i t e it <3 also when o d n a synthetic fibrous minerals, j if o na p rí ki ad glasná v 1 a k n a r different lengths. which can also to be laminated. Ja c o r g a n i c k a fillers comes to ú scales on the spot a lot of soot. me 1 and three i η , k a 1 a f u n a ,

cyclopentadienyl resin and polymers grafted on a styrene-acrylic nitrile base, which are produced by polymerizing acrylonitrile mixtures on polyoxy and polyoxyl-polyols analogously to the data in German patent documents 11 11 394, 12 22

669, (US 3,304,273, 3,383,351, 3,523,093), 11,52,536 (GB 1

040 452) and 11 52 537 (GB 987 618) and then they can be changed as follows:

polyoxyalkylene polyols or polyamines, in which aqueous polymeric polyoxyalkylene polyols or inorganic and organic fillers are used or as a mixture.

dispersion converts to

-po i yami new dispersions, can be used individually

Inorganic and/or organic fillers may be incorporated into the reaction mixture of preferred 3 to (a) to (d).

i for example in the amount of 0.5 and:

mass t n mass, based on the weight of the components

Suitable fire-fighting agents are, for example, tris-cresyl phosphate, tris-2-chloroethyl phosphate, tris-chloropropyl phosphate and tris-2,3-dibromopropyl phosphate.

In addition to the already mentioned halogen-substituted phosphates, they can be used to ensure fire resistance

-25 • · · ·· · ·· ·· ·«· ··· ··«· • ··· · ·*·· 9 * · · • · 9 9 9 9 9 9 9 999 9 9

9 9 9 9 9 9 9 9 9

99 99 99 ·· · · 99 arov©ho tě1 ©sa an organic pro tipo ř a rni prřd © d kv, iakok ¹ - ^a <' yd ratován ý oxidh í init ý , oxide antimon i v , oxidenapri κ ladarsenit ý , melamine, mixtures of melamine, expanded ammonium polyphosphate. Generally υo i vforfo reč nan amo ηny sulfate væoenat:

expanded graphite or a mixture thereof, for example graphite and/or ethylene glycol, is used in an amount of 5 to 50 parts by weight, preferably 5 to 25 parts by weight of said fire retardant for components (b) to (d).

100 wt.

More detailed information on auxiliary agents, for example from the monograph High Polymers, volume of the above-mentioned other usual ones can be found in the professional literature, by J.H. Saunders and K.C. Frisch XVI, Polyurethanes, parts 1 and 2, Interscience Publishers 1962, or 1964, or from the Kunststoff-Handbueh, Polyurethane, volume VII, Hanser-Verlag, Munich, Vienna, 1st and 2nd editions, 1966 and 1983.

The microcellular PU elastomers according to the invention are preferably produced by a low-pressure process or, in particular, injection molding in an open or, preferably, closed mold. The reaction is carried out, in particular, after sealing in a closed mold.

The injection molding technique is described, for example, by Röhr in the publication “Integra 1schaumstoffe,

Hans ©r-Ve r1 ag. J. L. Whart o ne m 1 9 7 5 , s t r any mn i cho v, in J o u r n a 1 to 98

Vienna 1975, by C e i 1 u 1 a r a U K n i ppem

P 1 asti c s , March/April 1973, pages 76 to 84.

Η. P i e c ho t o u a H. , Car 1 D.J. Prepelkou a P l a s t i c s publishing house, M a r s h / A p r i b © n in Journal of Ce l 1u1 ar

When using a mixing chamber with multiple inlet nozzles, the starting components can be fed individually and mixed intensively in the mixing chamber. It seems advantageous to work with a two-component process.

• 00 ·· 00 ·· 00 00 · · 0 0 0 0 0 0 • 000 · · 00· 0 0 0 00 ·· · 0 0 0 0 00 0·· 0 0 000 0000 000

000 00 ·0 00 0000

from 1 e v e r t h e advantageous or o n d a n d with her ρ r v e in v o r y pr « po 1yme r Contents N C O groups. 3 t rn s e at s c i e d i n g i. e o i o t á o h A 0°C to 150 ° C , a d e p r i e s t n e 1 i 0 ⁰ C and z 1 5 0 °C to r e action about also proportional to i o t h e n i n g in b ) , p ř it is strong 5 first of all he messed up with her ek u 1 á r n i rn i p r o f o u r e s p r o d 1 o u ž e n i r s t ě from what a / n o

with ss:i ovating agents c) and with cyanide components

4.4'~MDI

a), consisting essentially of fixed until the theoretical NCO content is reached.

The driving means d) and also any other auxiliary means and/or additional ones are usually combined into reinforcing components.

catalysts e) t s f )

The production of microcellular shaped parts is carried out using exclusively water as a driving agent for chain extension at an NCO/OH ratio of 0.85 to

1.20 and also catalysts e) in the presence of auxiliaries and/or additives f), wherein the NCO prepolymer heated to 80 to 110 °C is intensively mixed with water, catalyst and auxiliaries and/or additives and in an amount corresponding to the desired density of the shaped part is placed in a heated, tightly closed mold. The shaped parts are cured for 10 to 40 minutes and then removed.

preferably means and

The mass is determined as kg/m ⁵ , with 1000 to 1400 kg of the reaction mixture obtained in the form of compact form •7/m ³ , especially at 10 0 0

in the box into shape with o u s t 1 s e 1 ace rn a d e n t i o n 250 up to 1400 body ace has density preferably

up to 1 2 0 0 kg / πΡ , microcellular shaped bodies 8 0 0 kg / rn ³ . at the temperature of compression it has a density of 300 to 1000 kg/rn ³ , preferably 35 0 to The starting components are usually placed in the mold, heated to 15 to 80 °C, preferably 30 to 85 °C. The mold temperature is 20 to 1 10 ⁰ C, preferably 35 to 95 ⁰ C. The degree of production of microcellular or cellular shaped bodies

1,1 and 8, preferably between 2 and 6.

·· ·· ·· • « · · ··· « · *·* • · » · · · a • · · · · a ·· ·· ·· *· »· a · · · a · · · ·· · · · • · · ·* *· '7 7

Compared to microcellular PU elastomers based on NDI, the internal pressure in the mold is significantly increased, up to 50%, in order to achieve the same foam density in the MDI-based PO elastomers according to the invention.

To improve the demoulding of the elastomer shaped bodies produced according to the invention, it appears advantageous to coat the inner surfaces of the mold at least at the beginning of the production process with conventional external mold release agents, for example based on wax or silicone or, in particular, with an aqueous soap solution. However, internal mold release agents have proven particularly effective and are therefore used, as are described, for example, in EP-A-180 74 9 (AU 85/474 98), EP-A-1 73 8 88 (US 4 84/03288 (EP-A-119 471) and WO 86/01215. The dwell time in the mold is on average 3 to 60 seconds, depending on the size and geometry of the shaped part.

EP-A-153 639, 519 965), WO

The microcellular PU elastomers produced according to the invention have a bulk density of 350 to 800 g/l and are preferably used as elastic and damping elements in the automotive industry and in technology.

Examples of embodiments, invention

The invention is further illustrated by the following examples.

Production of polymers containing NCO groups

100 parts by weight of previously dewatered linear polyether-polyester polyol with an average OH coefficient of 56 mg KOH/g, which is formed by a polycondensate of polytetrahydrofuran with an ad and a po, chan 0.3

-MDI. Syl • ·· ·· ·· ·· ·· ··· ··· · · · · * ··· · · ··· · · ·· • . ··. · · · · ··· · · ··* ···· ··· ··· ·· ·· ·· ** ··

- 28 average molecular weight was reacted at a temperature of 115

250 g/mol and acid at ⁰ C at constant mass fractions of trimethylolpropane and a prepolymer was obtained which has a content

8 hmo t n. d í1y 4.4' WCO 5.68

a) Production of shaped parts (comparison)

To 100 parts by weight of this prepolymer, which had previously been brought to a temperature of 90°C, 4.2 parts by weight of a crosslinking component with a water content of 26.7% by weight, consisting of a mixture of Stabaxol 1, a spherically hindered carbodimide known to the skilled person for hydrolysis protection, and ethoxylates of ricinoleic acid and oleic acid, were added with stirring.

0.05 parts by weight of Desmorapid PP, manufactured by Rhein-Chemie GmbH, were also added to the reaction mixture to catalyze the driving reaction and 0.2 parts by weight of silicone oil DC 193 from Air Products and Chemicals, lne. to improve the cell structure. After mixing for a total of 8 s, the reaction mixture was filled into a sealable mold, heated to 90 °C and cured for 25 min. After demolding the microcellular product, the molded part was left to stand for 24 hours to guarantee dimensional stability based on the resulting expansion effect. The material was then subjected to thermal curing at 110 °C for 16 hours.

The material produced in this way from microcellular PU elastomers does not have the structure according to the invention, since GPC signals are not observed in the region above 250,000 g/mol and melting does not occur in DSC at temperatures above 230 ^° C.

h) Production of a shaped part according to the invention

100 wt. identical conditions of the same prepolymer were reacted with 4.2 wt. parts * · ·· ·· ·· ·· • .·· · · · « ··«· · · ··· · ··· • · ··· ·· · ··· * « ··· ··*« · · I ···· ·· «· ·· ·· ··©crosslinking mixture according to example 1a) with the addition of 0.07 wt. parts of a mixture of ethoxylated oleic acid with ethoxylated units in composition 9 and n-alkylbenzenesulfonic acid monoethanolamine salt with alkyl residues Cg Hi g to C i. g i-tj-i . The reaction proceeds visually noticeably slower. The further step is then analogous to example 1a).

For products manufactured according to 1 a) and 1 b) were

DSC 7, firm P erkin ~E1me r 2 0 ⁰ C/rn in melting dia gr a my.

determined at a temperature sequence Furthermore, characteristic static characteristics were determined and GPC records were also made. Therefore, the tempered tests were dissolved in a mixture of N,N-di methyl formamide (DMF) with 1 percent di-n.....butylamine while stirring at a temperature of 90 °C. The dissolution time was 2 h, the concentration was 10 ..

These 10% solutions were chromatographed undiluted. Chromatography is carried out using DMF as the mobile phase on a column set with ultrastyragel 10 ^s A, 10 ⁴ A. 10 ³ A, 500 A, 100 A. At a retention time of 39.8 min. a zone appears next to the main zone at 48.2 min. After the addition of 0.1 mol of lithium chloride (0.1 mol Li Cl per 1 l of the whole solution) the zone at 39.8 min. disappears completely.

The zone at 39.8 min., which according to the table below indicates a molecular weight of over 250,000 g/mol, as well as the disappearance of this zone in the presence of LiCl, in this case 0.1 mol per liter, are characteristics of the structure according to the invention.

The results of the test with defined polymethyl methacrylate (P Μ MA) are shown in the following table:

Retention 1 hour min.

9.88

1.25 4 3.45

Molecular weight g/mol1.

810,000

530,000 280,000 • · • · ·· ·· ·· ·· « ·

- 30 Retention time

The molecular cup is carrying.

4 8.24 1 5 2 00 0 4 7.36 ρ g 100 5 3 .. 3 2 3 0 5 0 0 5 8 . 4 7 7 1 0 0 5 3.81 3 500 A p p l a t i o n 1 ogar i tmu mo .1 ar ní material s t i time arises between r e t s n c h n i d o b a m i 39.88 minutes trajectory line. In the chromatograph i and also j yet

for t i r ete η čin a 58.47 min. visible signal

a minor a r n i c h masses increasing h than 810,000 g/moí, which however may be under). e invention also referred to as v Θ t s i π θ z z 5 0 00 0 g/mol, which L and C1 disappear and characterizes s t r u c t u r e according to find out from u , a č k o 1 and in lies my mo c e j c ho vad area . Detection occurred and help measurement refractive index and /or ultraviolet ab s o r b c i p i 2 6 5 nm. Type detection has no effect fished connections with invention in 1 and in ..

Residual metal deformation In pressure was measured in the modification DIN 5 3 572 at 80 ⁰ C, after 9 7 hours and 60% compression at used d i s t a n c i n h elements o 18 mm high and about the size of a base areas f o r t e r s bodies 40 x 40 mm and its height is 30 mm

with a tolerance of 1 mm.

The calculation was performed according to the following equation ho -hs

DV Pà) -- x 100 °á ho -hi

it is the original height hi height trial h? higher trial

of the test body in mm of the body in the deformed state in mm of the body after relaxation in mm

Microcellular PU-elastomers produced according to examples 1 • · ···

-31 ·· ·· • · · • · ··· ·· ·· » · · «

I · · · • « · · « • · « ·· ··

b) about 16.3% by weight of urea.

The content of the assumption of a complete reaction of C 02 under 1 © urea was the reactants forming the following equation mi-i 2 o + mM ρ 1 - mc o 2

- _x i ₀₀ rrpo + mMDI + mKV + mu 2o - mco 2

rnp 0 according to the recipe, the amount used after 1yo1u mM D 1 the amount of 4,4'-MDI that is available available for reaction with in 0 d 0 u rn M DI according to the recipe, the amount used 4,4'-MDI rnc 0 .2 amount of CO produced in g at stochi ometric reactions he 2 0 amount of water used mKV amount of product used for extension ř © t š z c e and/or crosslinking agent

In example 1b) there are structures according to the invention, whereby the residual deformation in compression compared to the microcellular elastomers in example 1a, of the same chemical composition, but without these structures, is significantly reduced.

P r. í ..k 1. a. d.......2........a (according to the invention)

Production by 1 meter

The production of prepolymers containing linear polyester-polyesterpolyol occurs

NCO groups according to example u

1. 100 parts by weight of this

2 0 ⁰ C for 5 minutes of mixing and 33 parts by weight of 4,4'-MDI NCO content 4.78 1¾ by weight

after 1yo1 was reacted at temperature with 0.3 parts by weight of trimethylolpropane The resulting prepolymer has after the reaction • ·

99 99

9 9 9 9 9 9 9 9 • ·*· 9 9 999 9 999 ·· 9 9 9 9 9 9 9 9 999 9 9

9 9 9 9 9 9 9 9 9

999 99 99 99 99 99

- 3 2 Production of shaped parts

100 parts by weight of the orthopolymer were reacted with stirring and with the addition of 0.03 parts by weight of Desmorapid PP and also 0.2 parts by weight of silicone oil DC 133 with 2.84 parts by weight of a crosslinking mixture with a water content of 36.3% by weight consisting of Stabaxol 1, a mixture of ethoxylated oleic acid and ricinoleic acid, monoethanolamine salt of n-alkylsulfonic acid and sodium salt of sulfated castor oil and poured into a mold heated to 90 ^° C. After a molding delay of 25 min, the microcellular polyurethane was heated for 16 hours at 110°C after an intermediate period of 24 hours. The static and mechanical characteristics as well as the DSC melting diagram and GPC values were subsequently determined.

P r o d u c t of the invention found 13.4 X. and all the values higher or subjected to mass tests of urea. It has a lower urea content equal to 14 Si by mass.

consisted of numerically therefore essential characters with respect to the recommended

E.ř.í.. k..l. and d.......2b (according to the invention)

Production of polymer

Production The NCO of the polymer was done by example 2 and with a difference ; rn. that in place of 33 wt. .. parts 4,4'- -MDI was already i t 0 37 wt. parts i z o k y a n a t c . P r e p o i yme r has after reaction to the content NCO

5.65 wt. %

Production of shaped parts

100 parts by weight of prepolymer, at a temperature of 90°C, was reacted with 3.1 parts of the mixture used in example 2a. Demoulding which was carried out on parts of the crosslinker and subsequent material

44

4 4 • ···

4 ·

4 4

444 4·

4 • ·

4 4

4

444 • 4

4·

4 4 4

4 4 4

4444 4

4 4

44

o p r The operations were carried out equally under 1 e p O p i S U U p ř í R 1 a d u 2 and . M i c r o c e l e n t i o n 1 vur e t ha n o v e c h s 1 a s t o m e r s . which I have 1 y by calculating urea content 1 5 , 7 The mass of . .. b y 1 y z j i š t e n y hundred tic, mechanical character e r i s t i c y, ratios melting was y

characterized by DSC and also tested by GPC.

In comparison with Example 2, a relative increase in GPC zone 5 values of more than 250,000 g/mol compared to the main zone, given by the polymer chain itself, at 100,000 g/mol was observed, and thus an increase in the structure according to the invention in the elastomer. This was also reflected in the DSC in a higher melting range and the resulting lower residual deformation in compression and also generally better mechanical characteristics.

Ex...p...a. (according to the invention, tempering after 30 minutes between glass1 and filling)

Production of WCO prepolymer

100 parts by weight of dewatered linear

polyether- polyesterpolyo. 1 in with 1 ozh en i m po p1e ρ říklad u 1 by 1 o mentioned in the text 115 ⁰ °C & from and intensive mixing to reaction with 0.3 parts by weight t r i rne this is 1 o 1 p r o p a n u a 3 8 G T 4 4 ' •MDI . Contents of NC,0 finished prepoi 1ymeru a n d i 1 based on measurement 5, 6 5% mass n. Formed part production 100 by weight part 1 s p r e p the polymer was reacted at the 90 OC with 3.1 weight day 1 year from the network a means of transport, whose

the composition corresponded to the reinforcing component according to example 2a, with the addition of 0.0 3 parts by weight of Desrno rapid PP and 0.2 • · • ·· • 9 • « · · • 9 9 • 9 9 9 9 9 • · · • · · · · · · • · 9 · • · · · · 9 9 ·9 • 9 · · · 9

9 9

9 9 9 weight of the three parts with Jikonove oil® DC 19 3 and was poured into tightly closed molds tempered at a temperature of 90 o C.

After a molding delay of 30 min. and a storage time of 30 min., the polyurethane molded part was molded at a temperature of 110 °C for 16 hours.

The microcellular polyurethane elastomers thus obtained had the usual static characteristics and DCS melting curves and GPC diagrams were also determined.

,Ε,Γ,ί.. k..l.,a, d 3 b (according to the invention, temperature controlled after 24 hours of storage)

The production of the NCO prepolymer and the fabrication of the molded part, including subsequent processing and characterization, were carried out as in Example 3a, with the only difference that the molding time was 24 hours.

P..ř.í.k,i..a.dy.......4 a........a........4 b

Production of copolymers containing NCO groups (according to the invention)

a) 100 parts by weight of a polyester mixture containing the same proportion of polycondensates from an equimolar mixture of monoethylene glycol and butanediol with an average molecular weight of 2000 g/mol were reacted at a temperature of 115 °C and under intensive stirring with 0.3 parts by weight of trichloropropane and 35 parts by weight of 4,4-MDI, to which 15 ppm of diethyl ether was previously added. The NCO content after the reaction was measured to be 5.12% by weight.

b) The synthesis of the prepolymer was carried out using the same amount of raw materials and identical process conditions as described in ·· ·· • 99 ·· • · · · · · • · · · 4 • 9 9 4 ·· ··

9 99

9 9 4

ex 1 a d u 4 and . 3 teams d i e t h y i e n g 1 y ko 1 - bis-chloromethane p r e p o 1yme r u makes 1 5.26 wt. Whirlwind both shapes of the body 4 b s t! s j n ýrn way both, while mentioned at 90 ⁰ C and behind a lot of d í 1 j/ from counting mixtures mass n parts crosslinking s rně s i

n o y i

NCO i i a carried out for example 4a and ! m o t n . parts p r e ρ o 1 y m e r u b y 1 o homogenization into the reaction with 2.82 > p s a n e and example 4 a and with 2.9 0 > written in example 4a. The reaction mixture was then poured into a mold heated to 90 °C. After a delay of 2 5 minutes, the mold was opened, the microcellular polyurethane molded part was removed and after storage for 24 hours, it was solidified for 16 hours at 110 °C. The reacted material.

which was numerically determined %, was tested in terms of its dynamic DSC melting characteristics.

amount of urea 14.6 wt.

its static-mechanical reductions, 6PC ratio and its

Example 4c (comparison)

The synthesis of the prepolymer is carried out according to Example 4b.

Production according to example 4a and whereby 100% of the homogenization mass is placed in a mold heated to ^900C .

The molding was carried out in contrast to 4b using the crosslinking mixture according to example 1, parts of the prepolymer were at 90 °C and with good reaction with 3.94 parts by weight and poured into the elastomer molding removed after a delay of 25 min in example 4b.

The form shall be processed and tested as specified in the log (comparison)

Production of NCO prepolymer • · • · · ··· • 9 9 ·

9 99

9 9 9

9 9

9 9 9

100 parts by weight of a dehydrated linear polyetherpolyesterpolyol of the composition according to Example 1 were reacted with 24 parts by weight of Desmodur 15 (naphthylene diisocyanate) at a temperature of 140°C under intensive homogenization. Desmodur 15 was metered in as a solid. The NCO content in the resulting prepolymer was 3.92% by weight.

Production of watches 1

100 mass of n. parts heated prepolymer on 90 ⁰ C add 0, 03 m o t n . of Desmorapi du's works and 0.2 mass n you are 1 icon 0 1e is DC 193 reacted with 2.9 mass n amplifier with me with also described in example 1. Reaction with me was

The part was then, as stated in the previous examples, poured into a mold heated to 90 °C. After a molding delay of 25 min., the molded part was set aside for 24 hours, then tempered for 15 hours at a temperature of 120 °C: it was subsequently tested for its characteristics.

mechanical

P.,Č...í...k..l..ad.y.......6 a........to........6 c (machine production)

Production of NCO preparatives

14000 parts by weight of a previously dewatered polyesterpolyol mixture containing ether groups, from 12838 parts by weight of a short-chain polytetrahydrofuran condensate with an average molecular weight of 250 g/mol and adipic acid and 1162 parts by weight of a polycondensate of the same short-chain polytetrahydrofuran, trimethylolpropane and adipic acid, the polyol mixing ratio being chosen such that the trimethylolpropane content in the entire polyol mixture was 3 g/1000 g, was reacted at a temperature of 115°C and with intensive stirring with 5320 parts by weight of 4,4'-MDI. The NCO content of the prepolymer in the prepolymer was 5.97% by weight.

• ·

a) Foaming was carried out with a low-pressure foaming machine at a mixing speed of 2700 rpm and a total discharge of 18.9 q/s. The mixing ratio of prepolymer to crosslinking components is 100:4.25.

The crosslinking mixture, which has a water content of 28.1%, consisted of Stabaxol 1, a mixture of ethoxylated oleic acid and ricinoleic acid, a C9 to C15 alkyl sulfonic monoethanolamine salt of sulfated castor oil. The crosslinking acid and sodium salt of the mixture were adjusted with respect to

Desmorapide

The reaction mixture of the prepolymer component added 0.03 wt. parts PP and 0.2 wt. parts silicone oil DC 193. was filled into tightly closed molds heated to 90 °C, which were opened after 30 min. After being set aside for a maximum of 30 min. the molded parts were tempered for 16 hours at a temperature of 110 ⁰ C.

b) The production of the prepolymer, the recipe and the conditions of the production method for the production of the shaped part correspond entirely to example 6a, except for the subsequent thermal treatment. Only the time has changed.

delay between demoulding and for 24 hours. tempering m, which was from above π and c) Recipe and production prepo1yme r u and also thermal subsequent processing correspond example 6a. However, it was done composition modification according to example 6a in that the crosslinking mixtures would 10 added 0 •for the strong mi chaní 0.02 wt. % 4,4'-MDI , related 0 per 100 parts by weight. Within 3 0 seconds n i k a gentle d i s p e r z e urea and the reinforcing agent is stable minimally 4 hours.

The urea content achieved with complete reaction of the isocyanate groups and with stoichiometric reaction is 0.017 parts by weight per

4.25 parts by weight of reinforcing components. The further production process of the shaped part, including additional processing, is carried out according to example 6a.

• · · • · · • 444 • 4 • ·

4 4 4 4

4» 44 44 44

4 4 4 4 4 4

4444 4 444

44 44 4444 4

4 4 4 4 4 4

44 44 44

For microcellular PU elastomers obtained according to Examples 6a to 6c, which contain a urea content of 16.3 wt.%.

In addition to recording DSC melting and usual static characteristic curves, GPC diagrams, dynamic tests were performed

The test spring has the shape of a cylinder with a height of 100 mm, an outer diameter of 50 mm and an inner diameter of 10 mm with three segmental constrictions. After loading the test spring with 6 KN over 100,000 load cycles at a frequency of 1.2 Hz, the reduction was measured as the difference between the output and input values of the spring height and was a measure of the compression strain during the fatigue test. The greater the compression strain reduction, the better the performance of the material under controlled conditions. The test for assessing the suitability of the material.

Example 7 (machine production ~ comparison)

Prepolymer production

14000 parts by weight of the previously dewatered polyol mixture of the composition according to Example 6a were reacted at a temperature of 115°C and with intensive stirring with 4900 parts by weight of 4,4'-MDI. The NCO content in the completely reacted polymer was 5.39% by weight.

Production of shaped parts

Foaming was carried out, analogously to Example 6a, with a low-pressure machine at a mixing speed of 2700 rpm and a discharge of 18.9 g/s.

The mixing ratio of prepolymer and crosslinking component was set to 100:4.28. The composition of the crosslinking mixture corresponded to example 1a. Before foaming, was added to the crosslinking mixture.

• · • · • · · · · · · · · • · · · · · 4 • ΦΦ · φφφφ φ φφφ φ ··· ΦΦ ·· ···· 4 ·· ····· Φ with regard to the prepolymer components, 0.03 Desmorapid P P and 0.2 parts by weight of silicone The reaction mixture was placed in molds heated to 90 °C, which were immediately closed. After a delay of 25 min. the molds were opened, the microcellular shaped body was set aside for 24 and was subsequently subjected to curing at 110 °C for 16 h.

mass of oil parts D C 193.

In addition to determining the static characteristics by DSC and GPC analysis, shrinkage was determined on the test springs under constant conditions.

The characteristics found are summarized in Tables 1 and 2.

in examples up to 7 are

JUDr. Petr KALENSKÝ attorney at law

JOINT LAW OFFICE VSETECKA ZELfcNÝ ŠVORČÍK KALENSKÝ AND PARTNERS

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0 • 0 0 0 • 00 • 0 • 00 • · · • · • · · 00 • 0 0 • · · 0 · • 0 0 • · · • · 0 0

- 40 Taboo 1 on 1

Examples 1 and compared to 1 point 2.a 2b 3a 3b 4 and 4b 4c s r o v— na η í 5 equal density • (g/ ^cm3 ) 0.5 0.5 1 0.5 0.5 0.52 0.52 0.5 3 0.5 1 0.53 0.49 tensile strength (N/mm ² ) DIN 53 571 3.6 3 , 8 3.4 4 4 4 _ø 2 5.4 4.7 4.9 3.4 elongation % DIN 53 571 540 500 470 480 405 450 5 13 5 1 3 578 340 resistance to further tearing N/mm DIN 53 515 16.5 17 13.7 17.3 1 7 2 1.1 22.5 20.6 20 13.5 residual compression set 22h, 80° C (%) 70 49 29 25 26 3 1 18 23 33 1 9 urea content (wt.) 16.3 16.3 13.4 15.7 16.3 16.3 14.6 14.6 14.6 9.7 DSC-area 132 148 135 138 149 139 139 1 50 1 1 8 — melting point (°C) until until until and 3 Of until until 3 Of until heating rate 20°/min 220 233 236 242 2 5.0 247 244 248 238

-41 — ··· ·· ·· 99 99

9 9 9 9 9 9

9 999 9 9 99

99 99 9999 9

9 9 9 9 9 9

9 9 9 9 9 9 9

Examples 1 a n d e s s e r v a n t 1 point 2 and 2b 3a 3b 4 and 4b 4 c comparison 5 comparison GPC signal not- ex i - exi - exist- exist- exist- exist- exist- no - ex ··· is given by η 1 i - e x i - stu- stu- stu- stu- stu- stu- stu- exist- stu- you pier- stu- is it is it is is is it is it is stu- it is in mass. is is >250000g/'mo 1 GPC signal — yes yes yes yes yes yes yes - yes is getting lost 0.1 m FACE

Table 2

Examples 6 and 6b 6c 7 comparison density (g/ ^cm3 ) 0.49 0.5 0.49 0.5 tensile strength (N/mm ² ) DIN 53 571 4.2 4.7 4, 4 3.8 elongation % DIN 53 571 480 520 470 550 resistance to further tearing N/mm DIN 53 515 13.8 15 13.5 14.4

• ·· ·· ·· ·· ·· ·· ·· ··· ··· • ··· ·

Examples 6a 6b 6 cents 7 comparison from the compression set -22h,80°C (¾) 1 5 26 1 3 29 dynamic reduction 100000 load cycles at 1.2 Hz, 6 KN load 12.2 17.8 11.8 >20 DSC-melting range (°C) heating rate 20°C/min 143-242 149-242 146-245 113-209 GPC signal with apparent molar mass >250000 g/mol exists exists exists does not exist GPC signal is lost at 0.1 m LiCl yes yes yes

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Claims (2)

PATENT CLAIMS A microcellular polyurethane elastomer containing urea groups based on (a) isocyanate components consisting of 4,4 'diphenylmethane diisocyanate with b) at least one oligomeric polyhydroxy compound with an average molecular weight of 1000 to 5000 g / mol and a functionality of 1.7 to 3, (c) optionally low molecular weight chain extensions and / or crosslinking agents; and (d) propulsion means; and (e) catalysts and, where appropriate f) auxiliaries and / or additives having a urea content of 14 to 18% by weight, which is defined by the amount of urea with the general formula C 14 Hi 2 ON? percent from diphenylmethane diisocyanate and a physico-chemical structure which, in addition to the low molecular weight main signal, is characterized by a signal from at least one zone at an apparent molecular weight of more than 250 000 g / mol, measured by gel permeation chromatography from a microcellular polyurethane elastomer solution at 90 DEG C. in N, N-dimethylformamide with 1'-di-n-butylamine, with respect to polymethylmethacrylate as standard, which decreases or is lost after the addition of lithium chloride to this solution and can be prepared by the addition of Bronstedt's or Lewis acid by reagents in an amount of 0.01 to 5% by weight, based on the weight of components a), b), e) and optionally c). A process for the production of a microcellular polyurethane elastomer containing urea groups according to claim 1 by the reaction of ·· ·· • · «> · ·· • · · · 4 • · ·· · ♦ • · · · · · (a) isocyanate components consisting of 4,4 'diphenylmethane diisocyanate with b) at least one oligomeric polyhydroxyl compound with an average molecular weight of 1000 to 5000 g / mol and a functionality of 1.7 to 3, c) optionally low molecular weight chain extensions and / or crosslinking agents; and (d) propulsion means; and (e) catalysts and, where appropriate f) auxiliaries and / or additives, in closed forms, characterized in that Bronstedt or Lewis acid reagents are added in an amount of 0.01 to 5% by weight, based on the weight of components a), b) or c. ) and is carried out for 8 to 24 hours e) and the duration of the polyurethane group. elastomer at a temperature of 100 to 120 ° C after tempering the microcellular containing urea Process according to Claim 2, characterized in that Bronstedt's or Lewis's acidic reagents are added in an amount of 0.05 to 2% by weight, based on the weight of components a), b), e) and optionally c). The process according to uses is a salt of claim 2 or 3, from monoethanolamine, characterized in that a n-alkylbenzenesulfonic acids with alkyl radicals C9 H19 to C15H31. Process according to one of Claims 2 to 4, characterized in that components a), d), e) and optionally f) contain 0.05 to 5% by weight. urea groups. Process according to one of Claims 2 to 5, characterized in that the oligomeric polyhydroxyl compound with an average molecular weight of 1000 to 5000 g / mol of component b) has a functionality of 2. ·· ·· »· · 1» · ·· • · · · «• ·« ·· ·· ·· ··· The use of microcellular polyurethanes containing urea groups according to claim 11. e1astomers, for production JUDr. Pst KftIBW lawyer JOINT LAW OFFICE VŠETECKA ZELfcNÝ ŠVORČÍK KALENSKÝ AND PARTNERS 120 00 Prague 2, Hálkova 2 Czech Republic